Josef Spreitz, Arnold E. Stütz and Tanja M. Wrodnigg
Crystalline 1,3,4,5-tetra-O-acetyl-6-bromo-6-deoxy-keto-d-fructose was prepared by reaction of 1,3,4,5-tetra-O-acetyl-d-fructopyranose with triphenylphosphane dibromide in dichloromethane. Subsequent deprotection followed by reaction of the free 6-bromodeoxyfructofuranose with sodium azide in N,N-dimethylformamide furnished the corresponding 6-azidodeoxyketose. Catalytic hydrogenation led to 1-deoxymannojirimycin in 27% overall yield from 1,3,4,5-tetra-O-acetyl-d-fructopyranose. This access is simple, inexpensive, high-yielding and clearly suitable for multigram preparations.